Photoinduced Enhancement of Chemical Shift Sensitivity to Local Vibrations
Abstract
The advent of novel free-electron laser sources enabling time-resolved X-ray photoelectron spectroscopy (tr-XPS) provides a unique opportunity to monitor local chemical environments in real time by measuring sub-eV shifts in core-electron binding energies. These shifts reflect the interplay between electronic excitation and nuclear motion, an interplay that remains largely unexplored. In our combined theoretical and experimental study of fluoropyridine (C5H4FN), we investigate this link by monitoring the evolving chemical environment at the N and F atomic sites as the photoexcited S1 state relaxes to the ground state via a conical intersection. We find that the F site responds primarily to vibrational relaxation, showing minimal sensitivity to the electronic excited state. In contrast, excitation to S1 induces a measurable energy shift at the N site and significantly enhances its sensitivity to local vibrations within the ring. This behavior arises from a photoinduced redistribution of charge, which also increases the Coulomb interaction between the 1s electron at the N atom and the atomic partial charge at an adjacent C atom. This insight opens new avenues for exploring ultrafast dynamics and conical intersection pathways in more complex systems, from photostable DNA bases to light-harvesting materials.
Related
- Sensitivity Enhancement of S-Band Rydberg Atom Microwave Receiver Enabled by Resonant Cavity Field Confinement
- Post-selected enhancement of phase sensitivity in a two-path interferometer
- Layered Cr2Ge2Te6 exhibits spin–phonon coupling and isotope-related pseudo-molecular vibrations
- Our sixth sense: Humans locate the source of ground vibrations with their feet
- Tunable parametric vibrations in fluid ferroelectric fibres
BibTeX
@article{gutierrez2026photoinduced,
title = {{Photoinduced Enhancement of Chemical Shift Sensitivity to Local Vibrations}},
author = {Ana Martínez Gutiérrez and Oliver Alexander and Pablo Estévez Alonso and Lorenzo Paoloni and Terry Mullins and André Al-Haddad and Thomas Baumann and Rebecca Boll and Christoph Bostedt and Simon Dold and Alberto de Fanis and Gianluca Geloni and Markus Ilchen and Iyas Ismail and Björn Lautenschlager and Tommaso Mazza and Dooshaye Moonshiram and Solène Oberli and Dawei Peng and Ralph Püttner and Svitozar Serkez and Marc Simon and Florian Trinter and Sergey Usenko and Michael Meyer and Jonathan Marangos and Jesús González-Vázquez and Daniel Rivas and Antonio Picón},
journal = {Journal of the American Chemical Society},
year = {2026},
month = jul,
doi = {10.1021/jacs.6c06538},
eprint = {2606.17776},
archivePrefix = {arXiv},
url = {https://hal.science/hal-05785837v1},
note = {CC BY},
}
RIS
TY - JOUR
TI - Photoinduced Enhancement of Chemical Shift Sensitivity to Local Vibrations
AU - Ana Martínez Gutiérrez
AU - Oliver Alexander
AU - Pablo Estévez Alonso
AU - Lorenzo Paoloni
AU - Terry Mullins
AU - André Al-Haddad
AU - Thomas Baumann
AU - Rebecca Boll
AU - Christoph Bostedt
AU - Simon Dold
AU - Alberto de Fanis
AU - Gianluca Geloni
AU - Markus Ilchen
AU - Iyas Ismail
AU - Björn Lautenschlager
AU - Tommaso Mazza
AU - Dooshaye Moonshiram
AU - Solène Oberli
AU - Dawei Peng
AU - Ralph Püttner
AU - Svitozar Serkez
AU - Marc Simon
AU - Florian Trinter
AU - Sergey Usenko
AU - Michael Meyer
AU - Jonathan Marangos
AU - Jesús González-Vázquez
AU - Daniel Rivas
AU - Antonio Picón
PY - 2026
DA - 2026/07/10
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c06538
UR - https://hal.science/hal-05785837v1
AB - The advent of novel free-electron laser sources enabling time-resolved X-ray photoelectron spectroscopy (tr-XPS) provides a unique opportunity to monitor local chemical environments in real time by measuring sub-eV shifts in core-electron binding energies. These shifts reflect the interplay between electronic excitation and nuclear motion, an interplay that remains largely unexplored. In our combined theoretical and experimental study of fluoropyridine (C5H4FN), we investigate this link by monitoring the evolving chemical environment at the N and F atomic sites as the photoexcited S1 state relaxes to the ground state via a conical intersection. We find that the F site responds primarily to vibrational relaxation, showing minimal sensitivity to the electronic excited state. In contrast, excitation to S1 induces a measurable energy shift at the N site and significantly enhances its sensitivity to local vibrations within the ring. This behavior arises from a photoinduced redistribution of charge, which also increases the Coulomb interaction between the 1s electron at the N atom and the atomic partial charge at an adjacent C atom. This insight opens new avenues for exploring ultrafast dynamics and conical intersection pathways in more complex systems, from photostable DNA bases to light-harvesting materials.
SN - 0002-7863
SN - 1520-5126
ER -